EP0824139B1 - Colles fusibles de copolyétherester - Google Patents

Colles fusibles de copolyétherester Download PDF

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Publication number
EP0824139B1
EP0824139B1 EP97113744A EP97113744A EP0824139B1 EP 0824139 B1 EP0824139 B1 EP 0824139B1 EP 97113744 A EP97113744 A EP 97113744A EP 97113744 A EP97113744 A EP 97113744A EP 0824139 B1 EP0824139 B1 EP 0824139B1
Authority
EP
European Patent Office
Prior art keywords
mol
hot melt
melt adhesive
adhesive compositions
diol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP97113744A
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German (de)
English (en)
Other versions
EP0824139A1 (fr
Inventor
Eberhard Dr.Rer.Nat. Kinkelin
Jürgen Dr.rer.nat. Spindler
Gerhard Dr.Rer.Nat. Poessnecker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Inventa AG fuer Forschung und Patentverwertung
Uhde Inventa Fischer AG
Original Assignee
EMS Inventa AG
Inventa AG fuer Forschung und Patentverwertung
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Filing date
Publication date
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Publication of EP0824139A1 publication Critical patent/EP0824139A1/fr
Application granted granted Critical
Publication of EP0824139B1 publication Critical patent/EP0824139B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C09J167/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences

Definitions

  • the invention relates to thermoplastic copolyether esters for hot melt adhesive applications.
  • the invention is particularly concerned with linear or branched, rapidly crystallizing and highly flexible copolyether esters based on terephthalic acid, 1,4-butanediol (BDO), diethylene glycol (DEG), or a mixture of diethylene glycol (DEG) and triethylene glycol (TEG) and one Polyethylene glycol (PEG) with an average molecular weight of 600 - 4000 g / mol.
  • BDO 1,4-butanediol
  • DEG diethylene glycol
  • TEG triethylene glycol
  • PEG Polyethylene glycol
  • EP-A-204 528 describes copolyester films for food packaging from a copolyester with at least 85 mol% terephthalic acid (TPS), 65 to 97 mol% butanediol (BDO) and 3 to 35 mol% of a polyethylene glycol (PEG) with a molecular weight of between 106 and 550 g / mol.
  • TPS terephthalic acid
  • BDO butanediol
  • PEG polyethylene glycol
  • the melting point at these products are between 160 and 200 ° C. Hot melt adhesive with such high Melting points are unusable for use in the textile sector.
  • DE-A-31 32 059 describes a polyetherester system for gluing textiles, consisting of terephthalic acid (TPS), ophthalic acid (IPS), butanediol and 10-25% of a polyalkylene ether diol with a molecular weight of 400-600 g / mol and with a melting point of 95-125 ° C.
  • JP 54/153835 also describes a hot melt adhesive for fibers made of TPS, IPS, butanediol and 1-10% polyalkylene glycol with a molecular weight of 300-6000 g / mol.
  • IPS is used to lower the melting point, which significantly worsens the crystallization properties.
  • DE-A-28 29 375 describes a thermoplastic mixed polyester consisting of TPS, another acid, 15-30 mol% ethylene glycol, diethylene glycol and 0.5-5 mole% polybutylene glycol.
  • TPS thermoplastic mixed polyester
  • another acid 15-30 mol% ethylene glycol
  • diethylene glycol diethylene glycol
  • polybutylene glycol 0.5-5 mole%
  • DE-A-44 30 048 describes a copolyester of TPS, IPS, butanediol and a mixture of diethylene glycol and triethylene glycol, the melting point is between 60 ° and 130 ° C.
  • thermoplastic block copolymers from TPS, butanediol and 1-7%, based on PBT, polyether with molecular weight from 600-6000 g / mol.
  • special polymer blocks are used Contrast to the statistical distribution used.
  • EP-A-0 164 910 describes copolyester films and hot melt adhesives described, which are contained in these films.
  • the copolyester hot melt adhesive have as components 80 to 97 mol% terephthalic acid and 3 to 20 mol% Isophthalic acid and as diol component 60 to 85 mol% 1,4-butanediol and 15 up to 40 mol% of diethylene glycol.
  • thermoplastic copolyetherester hotmelt adhesives with high Crystallization rate and high flexibility as a hot melt adhesive in technical applications for difficult substrates can be used.
  • the aim of the present invention was to develop relatively low-melting, Fast crystallizing and highly flexible products for hot melt adhesive applications.
  • the main advantage of a low melting point is the possibility to be able to use lower application temperatures. Most of all, this is important in the field of technical bonding when substrates, e.g. certain plastics are used, the melting temperatures below 150 ° C.
  • coated and glued parts can subsequently cause tension and subjected to deformations using conventional adhesives lose their adhesive properties and lead to substrate detachment.
  • a highly flexible adhesive is the only way to get a permanent one To connect materials.
  • the object of the invention is therefore, by a suitable combination of raw materials the three required properties "Relatively low melting point", “High Bring crystallization speed "and” high flexibility "in harmony and new hotmelt adhesives from a randomly constructed copolyetherester based on terephthalic acid and a mixture of aliphatic diols to provide.
  • the solution to the above problem lies in particular in hotmelt adhesives statistically composed copolyetherester with a combination of Butanediol (BDO), diethylene glycol (DEG) and polyethylene glycol (PEG) and optional other linear or branched aliphatic diols and terephthalic acid (TPS) as the only acid component.
  • BDO Butanediol
  • DEG diethylene glycol
  • PEG polyethylene glycol
  • TPS terephthalic acid
  • the melting points are generally far above the desired range.
  • a lowering of the melting point is possible by a partial replacement of the terephthalic acid with another acid, such as isophthalic acid (IPS).
  • IPS isophthalic acid
  • such a combination deteriorates the crystallinity or the rate of crystallization to a considerable extent.
  • diethylene glycol as a codiol component or a mixture of diethylene glycol and triethylene glycol enables the melting point to be lowered by more than 80 ° while at the same time maintaining the high rate of crystallization.
  • EP-A-204 528 describes a copolyester film made from 85-100 % TPS, 65-97% butanediol and 3-35 mol% polyethylene glycol with one Molecular weight of 106-550 g / mol and a melting point of 160 ° -200 ° C.
  • the polyethylene glycol according to the invention closes the molecular weight range of the polyethylene glycol, the polyethylene glycol according to the invention not one and the melting range is due to the application for Adhesive films too high.
  • terephthalic acid alone is used as the acid component.
  • the molar proportion of butanediol is between 40 and 70 mol%, based on the total amount of diol, while the proportion of diethylene glycol is between 10 and 50 mol% and optionally the proportion of triethylene glycol is between 0 and 35 mol%.
  • a polyethylene glycol with a molecular weight of 600-4000 g / mol in the amount of 2-10 mol% is used as the higher molecular weight polyethylene glycol component.
  • the proportion of butanediol can be reduced by up to 3 mol% if a polyhydric alcohol component is used to increase the molecular weight of the polymer, for example trimethylolpropane or optionally also a ⁇ -hydroxyalkylamide.
  • a polyhydric alcohol component for example trimethylolpropane or optionally also a ⁇ -hydroxyalkylamide.
  • the melting points of the copolyetherester hotmelt adhesives according to the invention are between 90 and 190 ° C, preferably between 100 and 180 ° C.
  • the melt viscosity, measured at 190 ° C and 2.16 kg load according to DIN / ISO 1133 is not less than 100 Pa * s, preferably not less than 200 Pa * s.
  • copolyetherester hotmelt adhesives according to the invention are based on their flexibility mainly in the hot melt process, but can also in the known powder coating processes be used.
  • copolyether esters according to the invention should also be used other products are compared, with Examples 9 as a comparative example serves that is not covered by the present invention.
  • the melting points, glass transition temperatures and cold crystallization points were included a DSC device from duPont Type 1090B. As a melting point the maximum of the melting peak is assumed as the glass transition temperature Middle of the two baselines. The maximum of is considered the cold crystallization point Crystallization peaks during the 2nd heating of the sample in the DSC.
  • the melt viscosity was determined at 190 ° C and one after the run-out process Load of 2.16 kg determined according to DIN / ISO 1133.
  • the polyester obtained has a melting point of approx. 157 ° C, a TG of approx. 0 ° C and a melt viscosity, measured at 190 ° C and 2.16 kg load, of 400 Pa * s.
  • the polyesters were produced analogously to Example 1 and are summarized in Tables 1 and 2.
  • the DSC measurements were carried out on pre-dried material (24h / 70 ° C). 1 2nd 3rd 4th 5 Terephthalic acid (mol%) 100 100 100 100 100 100 He Butanediol (mol%) 57 52 60 64 67 Diethylene glycol (mol%) 35 40 32 28 25th Triethylene glycol (mol%) Polyethylene glycol 600 (mol%) 8th 8th 8th 8th 8th 8th Melting point (DSC, ° C) 157 120 168 176 186 Glass temperature (DSC, ° C) 0 1 4th 1 5 Cold crystallization point.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Claims (8)

  1. Masses de colles fusibles composées d'un ester de copolyéther de structure statique à base d'acide téréphtalique et d'un mélange de diols aliphatiques, caractérisées en ce que de l'acide téréphtalique est utilisé en tant qu'unique composé acide et que sa proportion molaire rapportée à la quantité totale d'acide est de 100 % en moles, en ce que le composé diol est une combinaison de butanediol, de diéthylèneglycol, de polyéthylèneglycol, et le cas échéant de triéthyléneglycol, la proportion molaire en butanediol étant inférieure à 75 % en moles, la proportion en diéthylèneglycol étant comprise entre 5 et 60 % en moles, la proportion en triéthyléneglycol étant comprise entre 0 et 40 % en moles, et en ce qu'il est utilisé au moins 2, et cependant au plus 10 % en moles, d'un composé de polyéthyléneglycol de poids moléculaire plus élevé d'une masse molaire de 600 à 4.000 g/mole rapportés aux quantités totales respectives d'acide et de diols de 100 % en moles, et en ce que le point de fusion des masses de colles d'ester de copolyéther se situe entre 90 °C et 190 °C.
  2. Masses de colles fusibles d'ester de copolyéther selon la revendication 1, caractérisées en ce que la proportion molaire en butanediol est de préférence située entre 40 à 70 % en moles rapportée à la quantité totale de diols de 100 % en moles.
  3. Masses de colles fusibles d'ester de copolyéther selon l'une des revendications 1 et 2, caractérisées en ce que la proportion molaire en diéthylèneglycol est de préférence comprise entre 10 et 50 % en moles, et la proportion molaire en triéthylèneglycol de préférence entre 0 et 35 % en moles, rapportées à la quantité totale de diols de 100 % en moles.
  4. Masses de colles fusibles d'ester de copolyéther selon l'une ou plusieurs des revendications 1 à 3, caractérisées en ce que, en cas d'utilisation simultanée de diéthylèneglycol et de triéthylèneglycol, le rapport molaire entre le diéthylèneglycol et le triéthyléneglycol est de préférence compris entre 5 : 1 et 1 : 3.
  5. Masses de colles fusibles d'ester de copolyéther selon l'une ou plusieurs des revendications 1 à 4, caractérisées en ce que pour l'augmentation de la viscosité de fusion, un diol trivalent ou polyvalent peut être utilisé à hauteur de 3 % en moles maximum rapportés à la quantité totale de diols.
  6. Masses de colles fusibles d'ester de copolyéther selon l'une ou plusieurs des revendications 1 à 5, caractérisées en ce que leur point de fusion se situe entre 100° et 180 °C.
  7. Masses de colles fusibles d'ester de copolyéther selon l'une ou plusieurs des revendications 1 à 6, caractérisées en ce que la viscosité de fusion mesurée à 190 °C et à une charge de 2,16 kg d'après ISO/-DIN 1133 n'est pas inférieure à 100 Pas, de préférence pas inférieure à 200 Pas.
  8. Utilisation des masses de colles fusibles d'ester de copolyéther selon l'une quelconque des revendications 1 à 7 pour le procédé hotmelt, ou pour les procédés de revêtements pulvérulents connus.
EP97113744A 1996-08-12 1997-08-08 Colles fusibles de copolyétherester Expired - Lifetime EP0824139B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19632473 1996-08-12
DE19632473A DE19632473C2 (de) 1996-08-12 1996-08-12 Copolyetheresterschmelzklebemassen

Publications (2)

Publication Number Publication Date
EP0824139A1 EP0824139A1 (fr) 1998-02-18
EP0824139B1 true EP0824139B1 (fr) 1999-12-01

Family

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EP97113744A Expired - Lifetime EP0824139B1 (fr) 1996-08-12 1997-08-08 Colles fusibles de copolyétherester

Country Status (6)

Country Link
US (1) US5869594A (fr)
EP (1) EP0824139B1 (fr)
JP (1) JP3165399B2 (fr)
DE (2) DE19632473C2 (fr)
ES (1) ES2139415T3 (fr)
TR (1) TR199700606A2 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19831366A1 (de) * 1998-07-13 2000-01-27 Inventa Ag Tiefschmelzende Copolyester- bzw. Copolyetheresterschmelzklebemassen
JP4576254B2 (ja) * 2005-02-04 2010-11-04 大日本印刷株式会社 建材用フィルム
US8288447B2 (en) * 2006-06-07 2012-10-16 Henkel Ag & Co. Kgaa Foamable compositions based on epoxy resins and polyesters
DE102007004102A1 (de) * 2007-01-26 2008-07-31 Evonik Degussa Gmbh Kristalline Copolyester mit guter Löslichkeit in nicht halogenierten Lösungsmitteln und ihre Verwendung
JP5332165B2 (ja) * 2007-09-28 2013-11-06 東洋紡株式会社 結晶性ポリエステル樹脂およびこれを用いた接着剤組成物
JP5181601B2 (ja) * 2007-09-28 2013-04-10 東洋紡株式会社 溶剤可溶型結晶性ポリエステル樹脂を用いた接着剤組成物、積層体並びにフレキシブルフラットケーブル
JP5799987B2 (ja) * 2013-07-19 2015-10-28 東洋紡株式会社 結晶性ポリエステル樹脂およびこれを用いた接着剤組成物
EP4192913A4 (fr) * 2020-08-10 2024-07-17 Ester Industries Limited Copolyétherester à faible fusion

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE787375A (fr) * 1971-08-09 1973-02-09 Du Pont Procede pour lier un fil a filaments multiples par revetement d'un copolyester elastomere
JPS5265588A (en) * 1975-11-26 1977-05-31 Toray Ind Inc Covered metal structures and manufacturing thereof
US4116925A (en) * 1976-06-14 1978-09-26 Gaf Corporation Poly(tetramethylene terephthalate)-polyether block
US4156774A (en) * 1977-07-07 1979-05-29 Ciba-Geigy Corporation Thermoplastic copolyesters, processes for their preparation and their use
JPS55164270A (en) * 1979-06-07 1980-12-20 Kuraray Co Ltd Laminate
DE3132059C1 (de) * 1981-08-13 1983-01-13 Dynamit Nobel Ag, 5210 Troisdorf Polyaetherester fuer das Verkleben von Textilien
JPS5911383A (ja) * 1982-07-09 1984-01-20 Toyobo Co Ltd ホツトメルト接着剤
JPS5978234A (ja) * 1982-10-28 1984-05-07 Toyo Seikan Kaisha Ltd ホツトメルト接着剤
JPH082950B2 (ja) * 1985-05-31 1996-01-17 株式会社クラレ 共重合ポリエステルフイルム
US4975477A (en) * 1989-04-07 1990-12-04 Eastman Kodak Company Polyester formulations for hot-melt wood adhesives
DE4430048C2 (de) * 1994-08-24 1997-10-09 Inventa Ag Copolyesterschmelzklebemassen und deren Verwendung

Also Published As

Publication number Publication date
TR199700606A3 (tr) 1998-07-21
JPH10182807A (ja) 1998-07-07
EP0824139A1 (fr) 1998-02-18
TR199700606A2 (xx) 1998-07-21
US5869594A (en) 1999-02-09
DE19632473A1 (de) 1998-02-19
ES2139415T3 (es) 2000-02-01
JP3165399B2 (ja) 2001-05-14
DE19632473C2 (de) 2000-06-29
DE59700788D1 (de) 2000-01-05

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